JP2006152435A - Agent for treating metal surface, method of treating surface of metallic material, and surface-treated metallic material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a chromium-free agent for treating a metal surface used for imparting excellent corrosion resistance, alkali resistance and blackening resistance, to provide a method of treating the surface of a metallic material, and to provide a surface-treated metallic material. <P>SOLUTION: An agent for treating metal surfaces which comprises an aqueous medium, and, incorporated therein, (A) a cationic urethane resin which is water-soluble or in an aqueous emulsion form, (B) a cationic polycondensation product obtained from a phenol compound and an aldehyde, (C) a zirconium compound, and (D) a compound containing at least one kind of metal selected from Li, Mg, Al, Ca, Mn, Co, Ni, Zn, Sr, W, Ce and Mo, further, a method for treating a surface, and a surface-treated metallic material. When the proportion of the urethane resin (A) is equal to or higher than that of the polycondensation product (B), yellowing resistance can be also improved. Further, by causing the silyl denaturation of the ingredient (A), and incorporating an acid ingredient (E) and a vanadium compound (F) and/or a silane coupling agent, a further improvement in film performances can be attained. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention is a sheet coil made of metal, excellent corrosion resistance on the surface of the molded product, excellent alkali resistance and excellent blackening resistance, and in some cases, can further provide excellent yellowing resistance and contains chromium. The present invention relates to a metal surface treatment agent, a metal surface treatment method, and a surface-treated metal material used for forming a non-coated film. More specifically, the present invention is excellent in corrosion resistance in molded products such as automobile bodies, automobile parts, building materials, parts for home appliances, castings, sheet coils, etc. made of zinc-based plated steel sheets, steel sheets, and aluminum-based metal materials. Surface treatment agent used to form a chromium-free film, surface treatment method, surface treatment, which can impart excellent alkali resistance and excellent blackening resistance, and, in some cases, excellent yellowing resistance It relates to metal materials.

  Metal materials such as galvanized steel sheets and steel sheets are oxidized and corroded by atmospheric oxygen, moisture, ions contained in moisture, and the like. Moreover, it may wash | clean with the degreasing agent which shows alkalinity after shaping | molding processing, and if it is not durable with respect to an alkali, it will discolor or corrode early under use. Furthermore, there are phenomena in which the plated steel material appears to turn black under certain circumstances at high temperatures and high humidity, all of which are caused by the deterioration of the plating layer metal material, and the quality when incorporated as various products. From the viewpoint of design, it is regarded as a problem. As a method for preventing such corrosion, a chromate film is conventionally deposited on a metal surface by bringing the metal material surface into contact with a chromium-containing treatment liquid such as chromate chromate to deposit a chromate film, or applying and drying. There is a method of forming a film. However, these inorganic chromate films alone exhibit short-term rust prevention properties in a relatively mild environment, but have insufficient corrosion resistance over a long period of time or in a more severe environment. Furthermore, if a sheet coil that has been treated with chromate alone is cut out and molded, the formed film is hard, brittle and poor in lubricity, so the film will not fall off and impair the appearance, and sufficient processing will not be possible. There is a problem that cracks occur and break. Therefore, in general, in order to satisfy all these performances, a two-layer process is performed in which a chromate film is formed on the surface of a metal material, and a resin film is further formed on the formed chromate film. In addition, the chromate film is insufficient in terms of performance, and the treatment liquid contains harmful hexavalent chromium, so it takes time and cost for wastewater treatment, and the formed film also contains hexavalent chromium. Because of its content, it tends to be avoided from the environmental and safety aspects.

  As an attempt to satisfy all the performances with a single layer treatment, resin chromate that forms chromate and a resin film at the same time has been studied, and a specific water dispersion or water-solubility is formed on the surface of the aluminum-galvanized steel sheet. A processing method (Patent Document 1) for applying a resin composition containing a resin and a specific amount of hexavalent chromium, an inorganic compound hexavalent chromium ion or hexavalent chromium ion and trivalent chromium ion, and specific emulsion polymerization conditions There is known a metal surface treatment composition (Patent Document 2) containing an acrylic emulsion polymerized in (1). However, as described above, although the hexavalent chromium contained in the film is in a very small amount, it has a property of gradually dissolving and has problems in terms of environment and safety.

  As a method of using a non-chromate treatment liquid not having chromium, a metal composition surface treatment polymer composition containing a phenol resin polymer having a specific structure and an acidic compound and a surface treatment method (Patent Document 3), Metal surface treatment agent and treatment method (Patent Document 4) excellent in anti-fingerprint property containing two or more kinds of silane coupling agents having different functional groups having different structures that can react with each other. Metal surface treatment agent and treatment method (Patent Document 5) containing a silane coupling agent and a phenol resin polymer having a specific structure, an organic resin such as an epoxy resin having at least one nitrogen atom, an acrylic resin, or a urethane resin Metal surface treatment agent containing molecule and specific polyvalent anion, treatment method and treated metal material (Patent Document 6), (1) Bisphenol A epoxy having specific structure Rust preventive agent containing shi resin, (2) Rust preventive agent containing phenol resin and other specific resins such as polyester in specific ratio, and treatment method and treatment using (1) and (2) Metal surface treatment agent, treatment method and treatment metal material containing metal material (Patent Document 7), phenolic resin compound having specific structure, vanadium compound, specific metal compound, and organic polymer as optional component (Patent Document 8), and a metal surface treatment agent, a treatment method, and a treated metal material (patents) containing, as essential components, a specific water-soluble resin or aqueous emulsion resin, a phenolic resin compound having a specific structure, and a specific metal compound Document 9) is known.

However, in the metal surface treatment that does not use chromium, the treatment liquid has the advantage of not containing hexavalent chromium, but the corrosion resistance is insufficient, and in particular, the corrosion resistance of the scratched part and the processed part is remarkably inferior to the chromate film. Also, blackening resistance has a disadvantage that its performance is insufficient in a hot and humid environment. In addition, the resin film is generally affected by heat and has the property of turning yellow or brown (yellowing), and has the disadvantage of discoloring due to the heat generated during welding and pressing. Yes. Therefore, at present, a non-chromate metal surface treatment agent that forms a film capable of simultaneously imparting excellent corrosion resistance, alkali resistance and blackening resistance, and in some cases even better yellowing resistance to a metal material surface is obtained. It is not done.
Japanese Patent Publication No.4-2672 Japanese Patent Publication No. 7-6070 JP 7-278410 A JP-A-8-73775 JP-A-9-241576 Japanese Patent Laid-Open No. 10-1789 Japanese Patent Laid-Open No. 10-60233 JP 2001-181860 A JP 2003-13252 A

  The present invention was made in order to solve the problems of the prior art, and has excellent corrosion resistance, excellent alkali resistance and excellent blackening resistance in metal materials, and even better yellowing resistance in some cases. It aims at providing the metal surface treatment agent which does not contain chromium used for providing, a metal surface treatment method, and a surface treatment metal material.

  As a result of intensive studies on the means for solving the above problems, the present inventors have found that cationic water-soluble or aqueous emulsion urethane resins, polycondensates of phenolic compounds and aldehydes, which are cationic, zirconium compounds And by treating the surface of the metal material with an aqueous surface treatment agent containing other specific metal compound as an essential component, a film having excellent corrosion resistance, excellent alkali resistance, and excellent blackening resistance can be obtained. The headline and the present invention were completed.

  That is, the present invention is a cationic water-soluble or water-based emulsion urethane resin (A) (hereinafter referred to as cationic urethane resin (A)), a polycondensate of a phenolic compound and an aldehyde, which is cationic (B ) (Hereinafter referred to as cationic phenol polycondensate (B)), zirconium compound (C), and Li, Mg, Al, Ca, Mn, Co, Ni, Zn, Sr, W, Ce and Mo. The present invention relates to a metal surface treatment agent comprising a compound (D) containing at least one metal (hereinafter referred to as a metal compound (D)) in an aqueous medium. By including a cationic urethane resin (A), a cationic phenol-based polycondensate (B), a zirconium compound (C) and a metal compound (D) in the metal surface treatment agent of the present invention, excellent corrosion resistance and excellent A film having alkali resistance and excellent blackening resistance can be formed on the metal surface.

In the above, the compounding ratio of the cationic urethane resin (A) and the cationic phenol polycondensate (B) is set to (A) :( B) = 99: 1 to 50:50 as a solid content mass ratio. In this case, in addition to the above properties, a film having excellent yellowing resistance can be formed on the metal surface.
In the above, when a cationic water-soluble or aqueous emulsion urethane resin modified with silyl is used as the cationic urethane resin (A), the corrosion resistance and alkali resistance of the formed film are further improved.
Moreover, it is preferable that at least one acid component (E) (hereinafter referred to as an acid component (E)) selected from an inorganic acid and an organic acid is blended in the metal surface treatment agent of the present invention. Corrosion resistance, alkali resistance and blackening resistance of the coating film are further improved. Moreover, it is preferable to mix | blend a vanadium compound (F) with the said metal surface treating agent of this invention, and, thereby, the corrosion resistance and alkali resistance of the membrane | film | coat formed are improved further. Moreover, it is preferable to mix | blend a silane coupling agent (G) with the said metal surface treating agent of this invention, and, thereby, the corrosion resistance and alkali resistance of the membrane | film | coat formed are improved further.

  The present invention also provides a surface treatment method for a metal material, characterized in that a coating film is formed on the surface of the metal material by applying the metal surface treatment agent to the surface of the metal material and then drying the surface. The present invention relates to a metal material having a film formed by use.

  By applying the metal surface treating agent of the present invention to a metal surface, it is possible to form a film having excellent corrosion resistance, excellent alkali resistance and excellent blackening resistance and, in some cases, further excellent yellowing resistance.

  “Cationic” in the cationic urethane resin (A) (that is, cationic water-soluble or water-based emulsion urethane resin (A)) to be blended in the metal surface treating agent of the present invention is a cationic functional group in the molecular structure. It means having. Examples of the cationic functional group include the following general formula (I), (II), (III) or (IV)

(Wherein R ¹ , R ² , R ³ , R ⁶ , and R ⁷ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, or 1 carbon atom. Represents a linear or branched hydroxyalkyl group having from 10 to 10, preferably from 1 to 6, and R ⁴ and R ⁵ are each independently a linear or branched alkylene group having from 2 to 10 carbon atoms, preferably from 2 to 6 carbon atoms. And A ⁻ and B ⁻ represent a hydroxide ion or an acid ion). The amount of the cationic functional group may be an amount that allows the cationic urethane resin (A) to exist stably in a dissolved or dispersed state in the metal surface treatment agent of the present invention.

Formula (I), in (II), (III) and ^{(IV), R 1, R} 2, R 3, R 6, and represented by ^{R 7,} the alkyl group having 1 to 10 carbon atoms, a methyl group , Ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, etc. Group, 2-hydroxyethyl group, 1-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 5-hydroxypentyl group, 6-hydroxyhexyl group, 7-hydroxyheptyl group, 8-hydroxyoctyl group, Examples thereof include a 9-hydroxynonyl group and a 10-hydroxydecyl group. In the general formulas (III) and (IV), R ⁴ and R ⁵ represent an alkylene group having 2 to 10 carbon atoms, such as ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group. , Octamethylene group, 2-ethyl-hexylene group, decamethylene group and the like. In general formulas (II) and (IV), the acid ions represented by A ⁻ and B ⁻ are inorganic such as halogen ions (chlorine ions, bromine ions, fluorine ions, etc.), sulfate ions, nitrate ions, phosphate ions, etc. Organic acid ions such as acid ions, acetate ions and formate ions can be mentioned.
The cationic urethane resin (A) used in the present invention is water-soluble or water-based emulsion.

  The cationic urethane resin (A) used in the present invention is required to have a cationic functional group as described above. The cationic functional group is a cationic phenol-based polycondensate (B) (that is, phenol). A polycondensate of a compound based on aldehydes and a cationic compound (B)), a zirconium compound (C) or a metal compound (D) (ie, Li, Mg, Al, Ca, Mn, Co, Ni, This contributes to compatibility with the compound (D)) containing at least one metal selected from Zn, Sr, W, Ce and Mo. The solubility or dispersibility of the cationic urethane resin (A) in water may be achieved based on the self-solubility or self-dispersibility of the resin in water, and may be a cationic surfactant (for example, alkyl quaternary). It may be achieved with the help of ammonium salts etc.) and / or nonionic surfactants (eg alkyl phenyl ethers etc.).

  As the cationic urethane resin (A), a part of polyol used in a urethane resin which is a polycondensation product of polyols such as polyols, polyether polyols and polyester polyols and aliphatic, alicyclic or aromatic polyisocyanates. As a urethane resin obtained by using a polyol having a (substituted) amino group or a polyol having a nitrogen atom in the main chain, a urethane resin in which the nitrogen atom of the urethane resin is quaternized with a quaternizing agent, etc. It is done.

  In the above, examples of the polyol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, neopentyl glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1 , 4-butylene glycol, hexamethylene glycol, bisphenol A, hydrogenated bisphenol A, trimethylolpropane, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl 2-ethyl-1,3-propanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-2,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 3- Methyl-1,5-pen Diol, 2-methyl-2,4-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 3,5-heptanediol, 1,8 -Aliphatic diol compounds such as octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, trimethylolethane, trimethylolpropane, hexitols, pentitols, Examples thereof include trivalent or higher aliphatic or alicyclic alcohol compounds such as glycerin, diglycerin, polyglycerin, pentaerythritol, dipentaerythritol, and tetramethylolpropane.

  In the above, as the polyether polyol, for example, ethylene oxide adducts such as ethylene glycol, diethylene glycol and triethylene glycol, propylene oxide adducts such as propylene glycol, dipropylene glycol and tripropylene glycol, ethylene oxide of the above polyol and And / or propylene oxide adduct, polytetramethylene glycol and the like.

  In the above, as the polyester polyol, for example, a direct esterification reaction and / or ester of the polyol and an ester-forming derivative such as a polyvalent carboxylic acid or its anhydride, halide, ester, etc. in an amount less than the stoichiometric amount. Those obtained by exchange reaction; those obtained by ring-opening lactones with the above polyols; polycarbonate polyols and the like. Examples of the polyvalent carboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, and 2-methyladipic acid. Aliphatic such as 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, dimer acid, hydrogenated dimer acid, etc. Dicarboxylic acids; cycloaliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid; tricarboxylic acids such as trimeric acid, trimesic acid, castor oil fatty acid trimer A tetracarboxylic acid such as pyromellitic acid. Examples of the ester-forming derivatives include acid anhydrides of these polycarboxylic acids; halides of the polycarboxylic acids such as chlorides and bromides; methyl esters, ethyl esters, propyl esters, isopropyl esters of the polyvalent carboxylic acids, And lower aliphatic esters such as butyl ester, isobutyl ester, and amyl ester. Examples of the lactones include lactones such as γ-caprolactone, δ-caprolactone, ε-caprolactone, dimethyl-ε-caprolactone, δ-valerolactone, γ-valerolactone, and γ-butyrolactone.

  In the above, as the polyol having a (substituted) amino group or the polyol having a nitrogen atom in the main chain, the following general formula (V) or (VI)

(Wherein R ¹ , R ² , R ⁴ , R ⁵ and R ⁶ have the same meaning as defined in the general formulas (I) and (III), and R ⁸ has 2 to 10 carbon atoms, preferably 2 to 6 carbon atoms). And a polyol represented by the formula: -NR ¹ R ² group is substituted on any carbon thereof. Specific examples of such polyols include N, N-dimethylaminodimethylolpropane, N-methyl-N, N-diethanolamine and the like. Examples of the quaternizing agent include R ³ Cl, R ³ Br, R ⁷ Cl, and R ⁷ Br (wherein R ³ and R ⁷ are as defined in the general formulas (II) and (IV)). Can be mentioned.

  Regarding the cationic urethane resin (A), examples of the aliphatic, alicyclic or aromatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate ester, hydrogenated xylylene diisocyanate, 1,4-cyclohexylene diisocyanate, 4 , 4′-dicyclohexylmethane diisocyanate, 2,4′-dicyclohexylmethane diisocyanate, isophorone diisocyanate, 3,3′-dimethoxy-4,4′-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenyl Examples include methane diisocyanate, phenylene diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate. Among these, tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate ester, hydrogenated xylylene diisocyanate, 1,4-cyclohexylene diisocyanate. When an aliphatic or alicyclic polyisocyanate compound such as 4,4′-dicyclohexylmethane diisocyanate, 2,4′-dicyclohexylmethane diisocyanate, or isophorone diisocyanate is used, the resulting film has excellent weather resistance. This is preferable.

  The cationic urethane resin (A) of the present invention may be a silyl-modified, cationic water-soluble or water-based emulsion urethane resin, and when such a silyl-modified urethane resin is used, the corrosion resistance and anti-resistance of the formed film. The alkalinity is further improved. This silyl modification is performed by using a silane coupling agent in the synthesis step of a water-soluble or water-based emulsion urethane resin, and a more specific modification method is not particularly limited. For example, polyols (partly (substituted) amino A polyol having a group or a polyol having a nitrogen atom in the main chain) and a silane coupling agent are reacted, followed by condensation polymerization of an aliphatic, alicyclic or aromatic polyisocyanate, (Using a polyol having a (substituted) amino group or a polyol having a nitrogen atom in the main chain) and a polycondensation product of an aliphatic, alicyclic or aromatic polyisocyanate with a silane coupling agent. Is called.

There is no restriction | limiting in particular about the kind of silane coupling agent at the time of carrying out silyl modification | denaturation, As a silane coupling agent, the silane coupling agent included by the below-mentioned silane coupling agent (G) can be used. A silane coupling agent having an amino group (primary or secondary amino group) or an epoxy group is preferable as a silane coupling agent for silyl modification.
The amount of the silane coupling agent used for the silyl modification is not particularly limited, but polyols (a polyol having a (substituted) amino group or a polyol having a nitrogen atom in the main chain) and an aliphatic group are used. In view of the above effect, it is preferably 0.05 to 10% by mass based on the total mass of the alicyclic or aromatic polyisocyanate and the silane coupling agent, and 0.5 to 5% by mass. Is more preferable in view of the above effect. There is no restriction | limiting in particular about the reaction temperature at the time of making a silane coupling agent react, For example, what is necessary is just to react at 0-50 degreeC.

  The reason why the corrosion resistance and alkali resistance are improved by the silyl modification is not clear, but by making the silyl modification, the adhesion of the cationic urethane resin (A) to the metal substrate is increased, and further, oxygen, chlorine, etc. It is presumed that the barrier property is increased by suppressing the permeation of the corrosion factor.

  Among the above-mentioned cationic urethane resins (A), soap-free products that do not use a surfactant as a solubilizer or emulsifier that may adversely affect the adhesion of the film to the metal material and the water resistance of the film Or the thing which restrained the usage-amount is more preferable.

  The weight average molecular weight of the cationic urethane resin (A) is preferably 1,000 to 1,000,000, and more preferably 2,000 to 500,000. When the molecular weight is less than 1,000, the film-forming property is insufficient. On the other hand, when the molecular weight exceeds 1,000,000, the stability of the treatment agent tends to decrease.

  “Cationicity” in the cationic phenol polycondensate (B) (that is, a polycondensate of a phenolic compound and an aldehyde that is cationic (B)) contained in the metal surface treatment agent of the present invention "Means having a cationic functional group. Examples of the cationic functional group include those represented by the general formula (I) or (II). The cationic phenol-based polycondensate (B) only needs to have at least one kind of such a cationic functional group. These cationic functional groups are used, for example, when ammonia or amine corresponding to the cationic functional group represented by the general formula (I) is coexisted when polycondensation of a phenolic compound and an aldehyde. If necessary, it can be introduced by quaternizing the nitrogen atom with a quaternizing agent. The ratio of the cationic functional group contained in the cationic phenol polycondensate (B) is preferably 0.2 to 3 per benzene ring contained in the cationic phenol polycondensate (B). If the above numerical value is less than 0.2, the stability of the metal surface treatment agent tends to decrease, and if it exceeds 3, the corrosion resistance of the formed film tends to decrease. The cationic phenol polycondensate (B) used in the present invention is preferably a novolak type phenol polycondensate obtained by carrying out the above polycondensation reaction in the presence of an acidic catalyst. In addition, the cationic phenol polycondensate (B) used in the present invention is the above-mentioned novolak type phenol polycondensate modified with boron, silicon, phosphorus, heavy metal, nitrogen, sulfur, oil, rosin and the like. It may be modified by a known method.

  The phenolic compound used to obtain the cationic phenol polycondensate (B) used in the present invention is an acidic catalyst and the presence of ammonia or amine corresponding to the cationic functional group represented by the general formula (I). There is no particular limitation as long as it can be polycondensed with aldehydes to give a cationic phenol polycondensate (B). Examples of such phenolic compounds include phenol, m-cresol, m-ethylphenol, m-propylphenol, m-butylphenol, p-butylphenol, o-butylphenol, resorcinol, hydroquinone, catechol, 3-methoxyphenol, 4-methoxyphenol. 3-methylcatechol, 4-methylcatechol, methylhydroquinone, 2-methylresorcinol, 2,3-dimethylhydroquinone, 2,5-dimethylresorcinol, 2-ethoxyphenol, 4-ethoxyphenol, 4-ethylresorcinol, 3- Ethoxy-4-methoxyphenol, 2-propenylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, 3,4,5-trime Ruphenol, 2-isopropoxyphenol, 4-pyropoxyphenol, 2-allylphenol, 3,4,5-trimethoxyphenol, 4-isopropyl-3-methylphenol, pyrogallol, phloroglicinol, 1,2,4 -Benzenetriol, 5-isopropyl-3-methylphenol, 4-butoxyphenol, 4-t-butylcatechol, t-butylhydroquinone, 4-t-pentylphenol, 2-t-butyl-5-methylphenol, 2- Phenylphenol, 3-phenylphenol, 4-phenylphenol, 3-phenoxyphenol, 4-phenoxyphenol, 4-hexyloxyphenol, 4-hexanoylresorcinol, 3,5-diisopropylcatechol, 4-hexylresorcinol, -Heptyloxyphenol, 3,5-di-t-butylphenol, 3,5-di-t-butylcatechol, 2,5-di-t-butylhydroquinone, di-sec-butylphenol, 4-cumylphenol, nonylphenol 2-cyclopentylphenol, 4-cyclopentylphenol, bisphenol A, bisphenol F and the like. These may be used alone or in combination of two or more. Of these, phenol, o-cresol, m-cresol, p-cresol, bisphenol A, 2,3-xylenol, 3,5-xylenol, m-butylphenol, p-butylphenol, o-butylphenol, 4-phenylphenol, resorcinol Phenol and bisphenol A are most preferable.

  The aldehydes used for obtaining the cationic phenol-based polycondensate (B) used in the present invention are an acidic catalyst and ammonia or an amine corresponding to the cationic functional group represented by the general formula (I). There is no particular limitation as long as it can be polycondensed with the phenolic compound to form a cationic phenolic polycondensate (B). Examples of such aldehydes include formaldehyde, trioxane, furfural, paraformaldehyde, benzaldehyde, methyl hemiformal, ethyl hemiformal, propyl hemiformal, butyl hemiformal, phenyl hemiformal, acetaldehyde, propylaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde. , Β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methyl Benzaldehyde, p-methylbenzaldehyde, p-ethylbenz Examples thereof include aldehydes and pn-butylbenzaldehyde. These may be used alone or in combination of two or more. Of these, formaldehyde, paraformaldehyde, furfural, benzaldehyde, and salicylaldehyde are preferable, and formaldehyde and paraformaldehyde are most preferable.

  Examples of the amine used to obtain the cationic phenol polycondensate (B) used in the present invention include monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, isopropylamine, diisopropylamine, n-butylamine, Di-n-butylamine, tri-n-butylamine, isobutylamine, diisobutylamine, sec-butylamine, n-amylamine, di-n-amylamine, tri-n-amylamine, sec-amylamine, sec-hexylamine, 2-ethylhexyl Amine, dioctylamine, ethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine, N, N-di Chill ethanolamine, N, N- diethylethanolamine, N- ethyl diethanolamine, N-n-butyl diethanolamine, N, N- di -n- butyl ethanolamine, N- methyl propanolamine, tri isopropanol amine. As the quaternizing agent, a quaternizing agent as described in the production of the cationic urethane resin (A) can be used.

  The acidic catalyst used for obtaining the cationic phenol-based polycondensate (B) used in the present invention is not limited to the following examples. For example, hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, Acid, butyric acid, lactic acid, benzenesulfonic acid, p-toluenesulfonic acid, tartaric acid, boric acid and the like or a salt with a metal such as zinc chloride or zinc acetate can be used. These may be used alone or in combination of two or more.

  The number average molecular weight of the cationic phenol polycondensate (B) used in the present invention is preferably in the range of 1,000 to 1,000,000, more preferably in the range of 2,000 to 100,000. preferable. When the number average molecular weight is less than 1,000, the barrier property (denseness) of the formed film is inferior, and the corrosion resistance and alkali resistance tend to decrease. When the number average molecular weight exceeds 1,000,000, the liquid surface treatment agent of the present metal surface treatment agent is stable. May be impaired.

The zirconium compound (C) contained in the metal surface treating agent of the present invention is an oxide, hydroxide, complex compound, salt with an inorganic acid or an organic acid, etc., and a cationic urethane resin (A). And it is preferable that it is a good compatibility with the cationic phenol polycondensate (B). Examples of the zirconium compound (C) include zirconyl nitrate ZrO (NO ₃ ) ₂ , zirconyl acetate, zirconyl sulfate, zirconyl ammonium carbonate (NH ₄ ) ₂ [Zr (CO ₃ ) ₂ (OH) ₂ ], zirconium acetylacetonate. Zr (OC (= CH ₂ ) CH ₂ COCH ₃ )) _4, hexafluorozirconic acid, or the like can be used. These zirconium compounds can be used alone or in combination of two or more.

  Metal compound (D) contained in the metal surface treating agent of the present invention (ie, at least one selected from Li, Mg, Al, Ca, Mn, Co, Ni, Zn, Sr, W, Ce and Mo) The metal-containing compound (D)) is an oxide, hydroxide, complex compound, salt of an inorganic acid or an organic acid, or the like, and the cationic urethane resin (A) and the cationic phenol-based polycondensation. It is preferable that the compound has good compatibility with the product (B).

Specific examples of the metal compound (D) include lithium nitrate, lithium phosphate, lithium fluoride, lithium hydroxide, lithium sulfate, lithium carbonate, lithium oxalate, lithium oxide, magnesium nitrate, magnesium sulfate, and magnesium carbonate. , Magnesium hydroxide, magnesium fluoride, ammonium magnesium phosphate, magnesium hydrogen phosphate, magnesium oxide, aluminum nitrate, aluminum sulfate, potassium sulfate aluminum, sodium aluminum sulfate, aluminum ammonium sulfate, aluminum phosphate, aluminum carbonate, aluminum oxide, aluminum hydroxide, aluminum iodide, calcium acetate, calcium fluoride, calcium phosphinate _{[Ca (PH 2 O 2)} 2], calcium nitrate, hydroxide calcium , Calcium oxalate, calcium oxide, calcium acetate, permanganic acid HMnO _4, potassium permanganate, sodium permanganate, dihydrogen phosphate, manganese _{Mn (H 2 PO 4) 2} , manganese nitrate Mn _{(NO 3)} 2, Manganese sulfate (II), (III) or (IV), manganese fluoride (II) or (III), manganese carbonate, manganese acetate (II) or (III), ammonium manganese sulfate, manganese acetylacetonate Mn (OC (= CH ₂ ) CH ₂ COCH ₃ )) ₃ , manganese iodide, manganese oxide, manganese hydroxide, cobalt chloride, chloropentaamminecobalt chloride [CoCl (NH ₃ ) ₅ ] Cl, hexaamminecobalt chloride [Co (NH _{3) 6]} Cl _2, chromium, cobalt sulfate Barth, cobalt ammonium sulfate, cobalt nitrate, cobalt oxide dialuminum CoO · _Al 2 _{O 3,} cobalt hydroxide, cobalt phosphate, nickel nitrate, nickel sulfate, nickel carbonate, nickel acetylacetonate _{Ni (OC (= CH 2)} CH 2 COCH ₃ )) ₃ , nickel chloride, hexaammine nickel chloride [Ni (NH ₃ ) ₆ ] Cl ₂ , nickel oxide, nickel hydroxide, zinc sulfate, zinc carbonate, zinc chloride, zinc iodide, zinc acetylacetonate Zn _{(OC (= CH 2) CH} 2 COCH 3)) 2, dihydrogen phosphate, zinc, strontium nitrate, strontium sulfate, strontium carbonate, strontium chloride, strontium acetylacetonate _{Sr (OC (= CH 2)} CH 2 COCH 3) ) _2, Metatangu Ten acid _{H 6 [H 2 W 12 O} 40], ammonium metatungstate _{(NH 4) 6 [H 2} W 12 O 40], sodium metatungstate, paratungstate _{H 10 [W 12 O 46 H} 10], Ammonium paratungstate, sodium paratungstate, cerium oxide, cerium acetate Ce (CH ₃ CO ₂ ) ₃ , cerium (III) nitrate or (IV), cerium sulfate, cerium chloride, molybdenum oxide, molybdate H ₂ MoO ₄ , ammonium molybdate, ammonium paramolybdate, sodium molybdate, molybdophosphoric acid compounds (e.g., ammonium molybdophosphate _{(NH 4) 3 [PO 4} Mo 12 O 36] · 3H 2 O, sodium molybdophosphate _Na 3 _[PO 4 · 12MoO ] · NH ₂ O, etc.) and the like. Such metal compounds (D) can be used alone or in combination of two or more. About a molybdenum (VI) compound, a tungsten (VI) compound, and a manganese (VI) compound, what was reduced using reducing agents, such as alcohols and organic acids, can also be used. Among these metal compounds, it is particularly preferable to use a compound of Mg, Ni, or Co in terms of improving corrosion resistance and blackening resistance.

  The metal surface treatment agent of the present invention comprising the above cationic urethane resin (A), cationic phenol-based polycondensate (B), zirconium compound (C) and metal compound (D) is applied onto the metal surface. The film obtained in this way has excellent corrosion resistance, alkali resistance and blackening resistance, but in this metal surface treatment agent, an acid component (E) (that is, at least one selected from inorganic acids and organic acids) is further added. By blending the acid component (E)), the corrosion resistance, alkali resistance and blackening resistance of the formed film can be further improved.

  As the inorganic acid as the acid component (E), water-soluble ones can be used. For example, orthophosphoric acid, metaphosphoric acid, phosphonic acid, polyphosphoric acid (especially orthophosphoric acid multimers such as pyrophosphoric acid and triphosphoric acid, etc.) Phosphoric acid; hydrofluoric acid; fluorometallic acids such as fluorozirconic acid and fluorotitanic acid; nitric acid; sulfuric acid and the like. As the organic acid, water-soluble ones having a carboxyl group or a sulfone group can be used. For example, acetic acid, propionic acid, oxalic acid, tartaric acid, malic acid, gluconic acid, tannic acid, formic acid, ascorbic acid Etc. These acid components (E) can be used alone or in combination of two or more. Of these, hydrofluoric acid, nitric acid, sulfuric acid, and phosphoric acid are particularly preferable. The acid component (E) is mainly responsible for etching the surface of the metal material when the metal surface treatment agent of the present invention comes into contact with the metal material, and the film adhesion by etching (adhesion to the metal surface). As a result, the corrosion resistance, alkali resistance and blackening resistance are further improved. In particular, nitric acid also has the effect of further improving blackening resistance under high-humidity conditions. In addition, the acid component (E) further improves the liquid stability of the metal surface treating agent of the present invention.

By further blending the vanadium compound (F) in the metal surface treating agent of the present invention, the corrosion resistance and alkali resistance of the formed film can be further improved. As the vanadium compound (F), a vanadium compound having an oxidation number of pentavalent, tetravalent or trivalent can be used. For example, vanadium pentoxide V ₂ O ₅ , metavanadate HVO ₃ , ammonium metavanadate, metavanadium Vanadium compounds having an oxidation number of 5 such as sodium oxide, vanadium oxytrichloride VOCl ₃ ; vanadium trioxide V ₂ O ₃ , vanadium dioxide VO ₂ , vanadium oxysulfate VOSO ₄ , vanadium oxyacetyl acetate VO (OC (═CH ₂ )) CH ₂ COCH ₃ )) ₂ , vanadium acetyl acetate V (OC (═CH ₂ ) CH ₂ COCH ₃ )) ₃ , vanadium trichloride VCl ₃ , phosphovanadmolybdate H _15-X [PV _12-x Mo _x O _{40 ] · nH 2 O (6 <} x <12, n <30) having trivalent or tetravalent oxidation such Banaji Compound-free, and the like. These vanadium compounds can be used alone or in combination of two or more.

It is preferable that the metal surface treatment agent of the present invention contains a trivalent or tetravalent vanadium compound as the vanadium compound (F) from the standpoint of further maintaining high corrosion resistance and alkali resistance. That is, the ratio of the trivalent or tetravalent vanadium compound in the vanadium compound (F) is (V ³⁺ + V ⁴⁺ ) / V (where V ³⁺ , V ⁴⁺ and V are vanadium compounds, respectively). (F) represents the mass of trivalent vanadium, the mass of tetravalent vanadium, and the total vanadium mass) in the range of 0.1 to 1.0, preferably 0.2 to 1.0. More preferably, it is most preferably 0.4 to 1.0.

  As a method for incorporating a trivalent or tetravalent vanadium compound into the metal surface treatment agent of the present invention, a trivalent or tetravalent vanadium compound as described above is used, and in addition, a pentavalent vanadium compound is preliminarily used as a reducing agent. What was used and reduced to trivalent or tetravalent can be used. The reducing agent used may be either inorganic or organic, but is preferably organic, for example, alcohols such as methanol, ethanol, isopropanol, and ethylene glycol; aldehyde compounds such as formaldehyde, acetaldehyde, furfural; acetylacetone, ethyl acetoacetate, di Carbonyl compounds such as pivaloylmethane and 3-methylpentanedione; organic acids such as formic acid, acetic acid, propionic acid, tartaric acid, ascorbic acid, gluconic acid, citric acid and malic acid; triethylamine, triethanolamine, ethylenediamine, pyridine, Amine compounds such as imidazole, pyrrole, morpholine, piperazine; acid amide compounds such as formamide, acetamide, propionamide, N-methylpropionamide; glycine, alanine, pyrroline, Amino acids such as glutamic acid; monosaccharides such as glucose, mannose and galactose; natural polysaccharides such as maltose, sucrose, starch and cellulose; aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1′-diphosphonic acid , Organic phosphoric acid such as ethylenediaminetetra (methylenephosphonic acid), phytic acid; natural polymers such as gallic acid, tannic acid, humic acid, ligninsulfonic acid, polyphenol; polyvinyl alcohol, polyethylene glycol, polyacrylic acid, polyacrylamide, Synthetic polymers such as polyethyleneimine and water-soluble nylon; and aminocarboxylic acids such as EDTA.

  The organic reducing agent not only has the effect of reducing the vanadium compound, but also significantly improves the stability of the vanadium compound in the treatment liquid, and maintains the excellent corrosion resistance imparting effect of the metal surface treatment agent of the present invention for a long time. Can be made. Moreover, since the organic reducing agent is effective in forming a uniform film, an improvement in corrosion resistance can be expected.

  By further blending the silane coupling agent (G) in the metal surface treating agent of the present invention, the corrosion resistance and alkali resistance of the formed film can be further improved. The kind of the silane coupling agent is not particularly limited. For example, vinyltrichlorosilane, vinyltris (β-methoxyethoxysilane), vinyltriethoxysilane, vinyltrimethoxysilane, γ- (methacryloyloxypropyl) trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, N- (β-amino Ethyl) γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyl G Silane, .gamma.-chloropropyl trimethoxy silane, and the like ureidopropyltriethoxysilane. These can be used alone or in combination of two or more. Among these, from the viewpoint of the above effects, it is preferable to use an epoxy group-containing silane coupling agent or an amino group-containing silane coupling agent, and it is more preferable to use both.

  Next, the usage-amount of each component in the metal surface treating agent of this invention is demonstrated. The blending ratio of the cationic urethane resin (A) and the cationic phenol polycondensate (B) blended in the metal surface treatment agent of the present invention is (A) :( B) = 99: 1 to 1:99 is preferred. When the blending ratio of the cationic phenol-based polycondensate (B) is less than 99: 1, the corrosion resistance of the formed film becomes insufficient. On the other hand, when the cationic urethane resin (A) is less than 1:99, Corrosion resistance and alkali resistance tend to be insufficient. When the ratio is within the range of (A) :( B) = 99: 1 to 50:50, in addition to the above-described effects, it is possible to impart excellent yellowing resistance to the resulting film. Was found. The ratio is more preferably (A) :( B) = 90: 10-60: 40. When the blending ratio of the cationic phenol polycondensate (B) exceeds 50:50, yellowing resistance becomes insufficient.

  When the total solid content of the cationic urethane resin (A) and the cationic phenol-based polycondensate (B) contained in the metal surface treatment agent of the present invention is 100 parts by mass, the blend of the zirconium compound (C) The amount is preferably 0.1 to 20 parts by mass as zirconium, and more preferably 1 to 10 parts by mass. When the compounding amount of the zirconium compound (C) is within the above range, sufficient corrosion resistance and liquid stability can be ensured.

  When the total solid content of the cationic urethane resin (A) and the cationic phenol polycondensate (B) contained in the metal surface treatment agent of the present invention is 100 parts by mass, the metal compound (D) (that is, , Li, Mg, Al, Ca, Mn, Co, Ni, Zn, Sr, W, Ce, and a compound containing at least one metal selected from Mo (D)) are mixed in two or more metals (two or more). When the metal is contained, the total metal) is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass. When the compounding amount of the metal compound (D) is less than 0.01 parts by mass, blackening resistance cannot be imparted to the metal surface, and when it exceeds 10 parts by mass, the barrier properties (denseness) of the film are lowered and the corrosion resistance is lowered. Will tend to.

  When the total solid content of the cationic urethane resin (A) and the cationic phenol polycondensate (B) contained in the metal surface treating agent of the present invention is 100 parts by mass, the acid component (E) (that is, The blending amount of at least one acid component (E) selected from inorganic acids and organic acids is preferably 1 to 30 parts by mass, and 5 to 20 parts by mass as the acid component itself without water. Is more preferable. When the said compounding quantity of an acid component (E) is 1-30 mass parts, corrosion resistance, alkali resistance, and blackening resistance can be improved further.

  When the total solid content of the cationic urethane resin (A) and the cationic phenol-based polycondensate (B) contained in the metal surface treatment agent of the present invention is 100 parts by mass, the composition of the vanadium compound (F) The amount is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass as vanadium. When the said compounding quantity of a vanadium compound (F) is 0.01-20 mass parts as vanadium, corrosion resistance and alkali resistance can further be improved.

  When the total solid content of the cationic urethane resin (A) and the cationic phenol polycondensate (B) contained in the metal surface treatment agent of the present invention is 100 parts by mass, the silane coupling agent (G) Is preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, and even more preferably 3 to 15 parts by mass. When the said compounding quantity of a silane coupling agent (G) is 0.5-30 mass parts as solid content, corrosion resistance and alkali resistance can further be improved.

  Furthermore, in order to improve the lubricity and workability of the formed film, the metal surface treatment agent of the present invention is blended with at least one selected from water-based waxes such as polyolefin waxes, ester waxes and hydrocarbon waxes. can do. When the total solid content of the cationic urethane resin (A) and the cationic phenol polycondensate (B) contained in the metal surface treatment agent of the present invention is 100 parts by mass, the amount of the aqueous wax is solid. It is preferable that it is 0.5-30 mass parts as a minute, and it is more preferable that it is 1-20 mass parts.

  The aqueous medium used in the metal surface treatment agent of the present invention is usually water, but a small amount (for example, 10% by volume or less of the entire aqueous medium) of alcohol, ketone, cellosolve water-soluble for the purpose of improving the drying property of the film. An organic solvent may be used in combination. In addition, surfactants, antifoaming agents, leveling agents, antibacterial and antifungal agents, coloring agents, and the like can be added as long as the liquid stability and film performance of the metal surface treatment agent of the present invention are not impaired.

  The lower limit of the total solid content concentration of the metal surface treating agent of the present invention is not particularly limited as long as the effects of the present invention can be achieved, but the upper limit is limited from the viewpoint of liquid stability. The total solid content concentration of the metal surface treatment agent of the present invention is preferably adjusted to a range of 0.1 to 40% by mass, more preferably adjusted to a range of 1 to 30% by mass, and 5 to 25% by mass. Most preferably, the range is adjusted.

Next, the surface treatment method of the present invention will be described.
The metal surface treatment agent and surface treatment method of the present invention are suitable for steel sheets such as cold rolled steel sheets, carbon steel sheets, silicon steel sheets, plated steel sheets, and aluminum-based metal materials. The plated steel sheet includes, for example, a zinc-containing plated steel sheet that has been subjected to a plating process such as electrogalvanization, hot dip galvanization, 55% aluminum galvanization, 5% aluminum galvanization, aluminum plating, iron galvanization. The aluminum-based metal material includes a metal material mainly composed of aluminum or an aluminum alloy such as a pure aluminum material, an aluminum alloy material, and an aluminum die cast material.

  The pretreatment step prior to the treatment with the metal surface treatment agent of the present invention is not particularly limited. Usually, an alkaline degreasing agent or an acidic agent is used to remove oil and dirt adhered to the metal to be treated before the main treatment. Washing with a degreasing agent, washing with hot water, washing with solvent, etc., and then adjusting the surface with acid, alkali, etc., if necessary. In cleaning the metal material surface, it is preferable to wash with water after cleaning so that the cleaning agent does not remain on the metal material surface as much as possible.

  The treatment with the metal surface treatment agent of the present invention is performed by applying the metal surface treatment agent and then drying. There are no particular restrictions on the application method, a roll coating method in which a treatment agent is roll-transferred and applied to the surface of a metal material, or a method of squeezing with a roll after pouring with a shower ringer or the like, or draining with an air knife, in the treatment liquid What is necessary is just to select suitably from the method of immersing a metal material in this, the method of spraying a processing agent on a metal material, etc. Since the solvent of this treatment agent is mainly water, the treatment liquid temperature is preferably 0 to 60 ° C, more preferably 5 to 40 ° C.

  For the drying step after applying the metal surface treating agent of the present invention, it is not necessary to accelerate the curing of the cationic urethane resin (A) and the cationic phenol-based polycondensate (B), and only removal of the adhering water is performed. Does not necessarily require heat and may be physically removed by air drying or air blowing, etc., but it accelerates the curing of the cationic urethane resin (A) and the cationic phenol polycondensate (B) or is coated by softening. In order to enhance the effect, it is necessary to heat and dry. The temperature in that case is preferably 50 to 250 ° C, more preferably 60 to 220 ° C.

The amount of the film formed is preferably 30 to 5,000 mg / m ² , more preferably 50 to 3,000 mg / m ² as the dry film mass. When the dry film mass is less than 30 mg / m ² , sufficient corrosion resistance and blackening resistance cannot be obtained, and when it exceeds 5,000 mg / m ² , adhesion to a metal material and yellowing resistance are reduced.

Next, the operation of the present invention will be described. In the metal surface treatment agent of the present invention, each component is presumed to have the following functions, but the present invention is not limited by the following presumption.
The metal surface treatment agent of the present invention reacts with the surface of the metal material to form a film with good adhesion in the process of being applied to the metal material and dried, and the resin component forms a film, thereby imparting excellent corrosion resistance to the material. It is thought to do. The cationic phenol-based polycondensate (B) and the zirconium compound (C) form a dense three-dimensional structure at the time of applying the treatment agent or in the heat drying process, and also react with and adhere to the metal surface. . At this time, the acid component (E) is contained in the metal surface treatment agent, so that the etching action is enhanced, and the reactivity with the metal surface is further increased, whereby a stronger film is formed at the interface with the metal surface. Formed.

  The reason why the film thus formed has excellent corrosion resistance is considered to be due to the metal surface barrier property (denseness) of the formed film, as well as the following. That is, the cationic phenol-based polycondensate (B) contained in the treatment agent of the present invention is a compound having a resonance stabilization structure, and zirconium compound (C), Mn, Co, Ni in the metal compound (D), The compound containing W, Ce or Mo and the vanadium compound (F) are transition metal compounds. The film formed with the cationic phenol-based polycondensate (B), the zirconium compound (C) and the compound containing Mn, Co, Ni, W, Ce or Mo, and the optional vanadium compound (F), By reacting and sticking to the metal surface, the distance is close enough to overlap the outer shell orbit of the material metal. As a result, it has the effect of delocalizing electrons generated by corrosion using the φ orbit. Therefore, it is considered that the surface potential is kept uniform and excellent corrosion resistance (not only the flat portion, but also the cut end face and the scratched portion) is imparted. As a conventional anti-corrosion mechanism of chromate film, self-repairing action in which soluble hexavalent chromium is dissolved and re-deposited on the exposed metal surface is generally said. The anticorrosion mechanism of the film is the same anticorrosion mechanism as the treatment agent of the present invention due to the high cationogenicity of chromium (high adhesion reactivity to the metal surface) and excellent delocalization action (of corrosion electrons). thinking.

In addition, the metal compound (D) forms a basic compound on the surface of the metal substrate, or inactivates the surface of the metal substrate by modifying the surface of the metal substrate, thereby preventing the blackening of the metal substrate. And improve corrosion resistance.
Also, the silane coupling agent (G) deactivates the silanol group produced by hydrolysis of the metal material when it adsorbs on the surface of the metal material (hydrogen bonding) and the metal material is placed in a corrosive environment, Moreover, silane coupling agents react with each other in the formed film to form siloxane bonds, thereby improving the barrier properties of the film, thereby improving the corrosion resistance and alkali resistance.

On the other hand, the cationic urethane resin (A) is formed on the film formed at the metal interface (that is, has a two-layer structure), and has an effect of improving the corrosion resistance by enhancing the barrier property (denseness). In addition, there is an effect of improving workability.
In addition, combining the cationic urethane resin (A) and the cationic phenol polycondensate (B) and limiting the ratio of the two improves water resistance, makes the film difficult to dissolve, and improves alkali resistance. Leads to.
Regarding yellowing resistance (heat resistance), the cationic phenol-based polycondensate (B) has an aromatic ring and thus tends to be discolored by heating, but the cationic urethane resin (A) and cationic By making the usage ratio of the phenolic polycondensate (B) equal to or greater than the amount of the cationic urethane resin (A), yellowing resistance is imparted while maintaining corrosion resistance, blackening resistance and alkali resistance. / Can be improved.

  Hereinafter, the present invention will be described by way of examples and comparative examples, but the present examples are merely examples and do not limit the present invention. Metal materials to be treated, components (A) to (G) and treatment methods (pretreatment and treatment of the present invention) used in Examples and Comparative Examples, evaluation methods, explanation of evaluation results, treatment agent compositions and treatment methods (tables) 1-6) and the evaluation results (Tables 7-10) are listed below in this order.

(1) Metal material to be treated I Electrogalvanized steel sheet (plate thickness: 0.8 mm)
II Hot-dip galvanized steel sheet (thickness: 0.8 mm)
III 5% aluminum galvanized steel sheet (thickness: 0.6 mm)
IV 55% aluminum galvanized steel sheet (thickness: 0.4 mm)

(2) Metal surface treatment agent component (2-1) Cationic urethane resin (A)
Cationic urethane resin (A1)
150 parts by mass of polyether polyol (synthesis components: tetramethylene glycol and ethylene glycol, molecular weight 1500), 6 parts by mass of trimethylolpropane, 24 parts by mass of N-methyl-N, N-diethanolamine, 94 parts by mass of isophorone diisocyanate and 135 parts by mass of methyl ethyl ketone A portion was placed in a reaction vessel and reacted for 1 hour while maintaining at 70 to 75 ° C. to produce a urethane prepolymer. Subsequently, 15 mass parts of dimethyl sulfuric acid was put into this reaction container, and it was made to react at 50-60 degreeC for 30 to 60 minutes, and the cationic urethane prepolymer was produced | generated. Next, 576 parts by mass of water was added to the reaction vessel to uniformly emulsify the mixture, and then methyl ethyl ketone was recovered to obtain a water-soluble cationic urethane resin (A1).

Cationic urethane resin (A2)
135 parts by mass of polyester polyol (synthesis components: isophthalic acid, adipic acid and 1,6-hexanediol, ethylene glycol, molecular weight 1700), 5 parts by mass of trimethylolpropane, 22 parts by mass of N-methyl-N, N-diethanolamine, 86 parts by mass of isophorone diisocyanate and 120 parts by mass of methyl ethyl ketone were placed in a reaction vessel and reacted for 1 hour while maintaining at 70 to 75 ° C. to produce a urethane prepolymer. 17 parts by mass of dimethyl sulfuric acid was placed in the reaction vessel and reacted at 50 to 60 ° C. for 30 to 60 minutes to produce a cationic urethane prepolymer. Next, 615 parts by mass of water was added to the reaction vessel to uniformly emulsify the mixture, and then methyl ethyl ketone was recovered to obtain a water-soluble cationic urethane resin (A2).

Cationic polyurethane resin (A3)
130 parts by mass of polycarbonate polyol (synthesis component: 1.6-hexane carbonate diol, ethylene glycol, molecular weight 2000), 4 parts by mass of trimethylolpropane, 21 parts by mass of N-methyl-N, N-diethanolamine, 75 parts by mass of isophorone diisocyanate and 115 parts by mass of methyl ethyl ketone was put in a reaction vessel and reacted for 1 hour while maintaining at 70 to 75 ° C. to produce a urethane prepolymer. Next, 22 parts by mass of dimethyl sulfuric acid was placed in the reaction vessel and reacted at 50 to 60 ° C. for 30 to 60 minutes to produce a cationic urethane prepolymer. Next, 633 parts by mass of water was added to the reaction vessel to uniformly emulsify the mixture, and then methyl ethyl ketone was recovered to obtain a water-soluble cationic polyurethane resin (A3).

Cationic polyurethane resin (A4)
Polyester polyol (synthesis components: isophthalic acid, adipic acid, 1,6-hexanediol and ethylene glycol, molecular weight 2000) 135 parts by mass, trimethylolpropane 5 parts by mass, N-methyl-N, N-diethanolamine 22 parts by mass, isophorone 86 parts by mass of diisocyanate, 1 part by mass of γ-aminopropyltriethoxysilane and 120 parts by mass of methyl ethyl ketone were placed in a reaction vessel, and reacted for 1 hour while maintaining at 70 to 75 ° C. to produce a urethane prepolymer. Next, 17 parts by mass of dimethyl sulfuric acid was placed in the reaction vessel and reacted at 50 to 60 ° C. for 30 to 60 minutes to produce a cationic urethane prepolymer. Next, 615 parts by mass of water was added to the reaction vessel to uniformly emulsify the mixture, and then methyl ethyl ketone was recovered and silyl-modified to obtain a water-soluble cationic polyurethane resin (A4).

Cationic polyurethane resin (A5)
150 parts by mass of polycarbonate polyol (synthesis components: 1,3-dioxolan-2-one and 1,6-hexanediol, molecular weight 1700), 6 parts by mass of trimethylolpropane, 24 parts by mass of N-methyl-N, N-diethanolamine, 94 parts by mass of isophorone diisocyanate, 2 parts by mass of N- (β-aminoethyl) γ-aminopropyltrimethoxysilane and 135 parts by mass of methyl ethyl ketone were placed in a reaction vessel and reacted for 1 hour while maintaining at 70 to 75 ° C. A polymer was produced. Subsequently, 15 mass parts of dimethyl sulfuric acid was put into this reaction container, and it was made to react for 30 to 60 minutes at 50-60 degreeC, and the cationic urethane prepolymer was produced | generated. Subsequently, 576 parts by mass of water was added to the reaction vessel, and the mixture was uniformly emulsified. Then, methyl ethyl ketone was recovered and silyl-modified to obtain a water-soluble cationic polyurethane resin (A5).

(2-2) Cationic phenolic polycondensate (B)
Cationic phenolic polycondensate (B1)
A 1000 mL flask equipped with a reflux condenser was charged with 1 mol (228 g) of bisphenol A and 0.3 g of p-toluenesulfonic acid as a catalyst, the internal temperature was raised to 100 ° C., and 0.85 mol (69 g) of an aqueous formaldehyde solution was added. The mixture was added over 1 hour and reacted at 100 ° C. for 2 hours under reflux. Thereafter, the reaction vessel is left to cool in water, and after the aqueous layer separated into the upper layer is no longer turbid, the aqueous layer is removed by decantation, and further heated and stirred until the temperature reaches 170 to 175 ° C. Water was removed.
Next, the temperature was lowered to 100 ° C., 234 g of butyl cellosolve was added to completely dissolve the polycondensate, 234 g of pure water was added, and when the temperature in the system dropped to 50 ° C., 1 mol of diethanolamine (75 g ) And 1 mol (81.1 g) of an aqueous formaldehyde solution was added dropwise at 50 ° C. over about 1 hour. Furthermore, the temperature was raised to 80 ° C., and the reaction was continued with stirring for about 3 hours to obtain a cationic phenol polycondensate (B1).

Cationic phenolic polycondensate (B2)
A 1000 mL flask equipped with a reflux condenser was charged with 1 mol of phenol (96 g) and 0.3 g of p-toluenesulfonic acid as a catalyst, the internal temperature was raised to 100 ° C., and 0.7 mol of an aqueous formaldehyde solution (56.8 g) Was added over 1 hour and reacted at 100 ° C. for 2 hours under reflux. Thereafter, the reaction vessel is left to cool in water, and after the aqueous layer separated into the upper layer is no longer turbid, the aqueous layer is removed by decantation, and further heated and stirred until the temperature reaches 170 to 175 ° C. Water was removed.
Next, the temperature was lowered to 100 ° C., 234 g of butyl cellosolve was added to completely dissolve the polycondensate, 234 g of pure water was added, and when the temperature in the system dropped to 50 ° C., N-methylpropanolamine 1 mol (89 g) was added, and 0.7 mol (56.8 g) of an aqueous formaldehyde solution was added dropwise thereto at 50 ° C. over about 1 hour. Furthermore, the temperature was raised to 80 ° C., and the reaction was continued with stirring for about 3 hours to obtain a cationic phenol polycondensate (B2).

Cationic phenolic polycondensate (B3)
A 1000 mL flask equipped with a reflux condenser was charged with 1 mol (108 g) of O-cresol and 0.3 g of p-toluenesulfonic acid as a catalyst, the internal temperature was raised to 100 ° C., and 0.85 mol (69 g) of an aqueous formaldehyde solution was added. ) Was added over 1 hour and reacted at 100 ° C. under reflux for 2 hours. Thereafter, the reaction vessel is left to cool in water, and after the aqueous layer separated into the upper layer is no longer turbid, the aqueous layer is removed by decantation, and further heated and stirred until the temperature reaches 170 to 175 ° C. Water was removed.
Next, the temperature was lowered to 100 ° C., 234 g of butyl cellosolve was added to completely dissolve the polycondensate, 234 g of pure water was added, and when the temperature in the system dropped to 50 ° C., N, N-diethyl 1 mol (117 g) of ethanolamine was added, and 1 mol (81.1 g) of an aqueous formaldehyde solution was added dropwise thereto at 50 ° C. over about 1 hour. Furthermore, the temperature was raised to 80 ° C., and the reaction was continued with stirring for about 3 hours to obtain a cationic phenol polycondensate (B3).

(2-3) Metal compound (C)
C1: ammonium zirconium carbonate C2: hexafluorozirconic acid

(2-4) Metal compound (D)
D1: lithium oxide D2: magnesium nitrate D3: magnesium oxide D4: aluminum acetylacetonate D5: calcium fluoride D6: cobalt nitrate D7: nickel nitrate D8: nickel carbonate D9: strontium nitrate D10: molybdenum oxide D11: ammonium metatungstate D12 : Cerium oxide D13: Zinc oxide D14: Zinc acetylacetonate
D15: Manganese carbonate D16: Manganese oxide

(2-5) Acid component (E)
E1: Hydrofluoric acid E2: Phosphoric acid E3: Nitric acid E4: Citric acid E5: Oxalic acid (2-6) Vanadium compound (F)
F1: ammonium metavanadate F2: vanadium acetylacetonate F3: vanadium phosphate F4: vanadium oxysulfate

(2-7) Silane coupling agent (G)
G1: Vinyltrimethoxysilane G2: γ-glycidoxypropyltrimethoxysilane G3: N- (β-aminoethyl) γ-aminopropyltrimethoxysilane G4: γ-aminopropyltriethoxysilane

(3) Treatment method (3-1) Degreasing
The material was degreased with Nippon Parkerizing Co., Ltd. alkali degreasing agent Pulclean 364S (20 g / L building bath, 60 ° C., 10 seconds spray, spray pressure 0.5 kg / cm ² ), followed by spray water washing for 10 seconds.
(3-2) Application and drying
I: A metal surface treatment agent (medium: water) adjusted to a solid content concentration of 10% by mass was applied by bar coating so that the dry mass was 700 mg / m ² and dried at 80 ° C. (PMT: ultimate plate temperature).
II: A metal surface treatment agent (medium: water) adjusted to a solid content concentration of 16% by mass was applied by bar coating so that the dry mass was 1000 mg / m ² and dried at 150 ° C. (PMT).

(4) Evaluation method In the following evaluation, it is understood that □ or more is practical.
(4-1) Corrosion resistance About the processed plate samples prepared in Examples and Comparative Examples, non-processed (planar part), cross-cut to reach the substrate with an NT cutter (cross-cut part), Erichsen 7 mm extruded (processed) Part) was subjected to a corrosion resistance test. The evaluation method is as follows.
(Plane) Based on the salt spray test method JIS-Z-2371, the white rust generation area after 360 hours of salt spray was determined and evaluated.
Evaluation criteria: White rust generation area ◎ <1%, ○ 1% to less than 5%, □ 5% to less than 10%, △ 10% to less than 30%, × 30% to less than 50%, XX 50% or more.
(Cross cut part) Based on the salt spray test method JIS-Z-2371, the occurrence of white rust after 360 hours of salt spray was evaluated with the naked eye.
Evaluation criteria: White rust occurrence status ◎ Almost no rust, ○ There are many parts where no white rust is generated in the cross cut part, △ All of the cross cut part is white rust, but there is no flow rust, × cross cut Rust occurs from the part.
(Processing part) Based on the salt spray test method JIS-Z-2371, the occurrence of white rust after 360 hours of salt spray was evaluated with the naked eye.
Evaluation criteria: White rust occurrence status ◎ Almost no rust, ○ Many white rust is not generated in the processed part, △ All of the processed part is white rust, but there is no flow rust, × flowing from the processed part Rust is generated.

(4-2) Alkali resistance After spraying a treated plate sample with an aqueous degreasing agent adjusted to 65 ° C. with an alkaline degreasing agent Parklean 364S manufactured by Nihon Parkerizing Co., Ltd. in 20 g / L water, and washed with water. And dried at 80 ° C. About this board, corrosion resistance was evaluated by the conditions and evaluation methods described in (4-1) above.
(4-3) Blackening resistance After the treated plate sample was left in an atmosphere of 70 ° C. and 95% humidity for 12 days, the appearance was observed and evaluated with the naked eye.
Evaluation criteria: No white rust, no black change, no white rust, black change slightly, Δ white rust occurrence, black change slightly, x white rust occurrence, black change considerably.
(4-4) Yellowing resistance After the treated plate sample was left in a 250 ° C. atmosphere for 2 hours, the appearance was observed and evaluated with the naked eye.
Evaluation criteria: ◎ No discoloration, ○ Slightly yellow, △ Whole yellowing, × Whole tan.

  Tables 1 to 6 show the compositions and processing methods of the metal surface treatment agents of Examples 1 to 109 and Comparative Examples 1 to 6, and Tables 7 to 10 show the test evaluation results. As is clear from Tables 7 to 10, the metal materials of Examples 1 to 50 and 52 to 109 having coatings formed using the metal surface treatment agent of the present invention have corrosion resistance, alkali resistance, blackening resistance and yellow resistance. It can be seen that since the modification is good and does not contain harmful chromium, the safety is high, and the flat part, the crosscut part, and the processed part all have excellent corrosion resistance equivalent to or better than the chromate treatment. Further, the metal material of Example 51 in which the ratio (A) / (B) was rich in (B) was inferior in yellowing resistance, but was excellent in corrosion resistance, alkali resistance and blackening resistance.

  Moreover, also about the comparison between Examples, the metal material of Example 7, 13 and 4 processed with the metal surface treating agent which mix | blended the acid component (E) which is an arbitrary component respectively mix | blends the corresponding acid component (E). The corrosion resistance, alkali resistance and blackening resistance were superior to those of the metal materials of Examples 19, 20 and 22 treated with the metal surface treatment agent that was not. Moreover, the metal material of Example 24 processed with the metal surface treating agent which mix | blended the vanadium compound (F) which is an arbitrary component is Example 36 processed with the metal surface treating agent which did not mix | blend a corresponding vanadium compound (F). Compared to these metal materials, the corrosion resistance and alkali resistance were excellent. Moreover, the metal material of Examples 52-77 processed with the metal surface treating agent which mix | blended the silane coupling agent (G), The example processed with the metal surface treating agent which mix | blended the silyl modified cationic urethane resin (A) The metal materials of Examples 94 to 109 treated with a metal surface treatment agent containing 78 to 93 metal material, a silyl-modified cationic urethane resin (A) and a silane coupling agent (G) have Alkali resistance was superior to the metal materials of the other examples, and depending on the combination, the corrosion resistance and alkali resistance of the crosscut part and the processed part were also superior to the metal materials of the other examples.

  On the other hand, the metal material of the comparative example 1 whose film does not contain the cationic urethane resin (A), and the comparative example where the film does not contain the cationic phenol polycondensate (B) which is an essential component of the metal surface treatment agent of the present invention. The metal material of No. 2, the metal material of Comparative Example 3 in which the coating does not contain the zirconium compound (C), and the metal material of Comparative Example 5 in which the ratio of (A) / (B) is outside the scope of the present invention are corrosion resistance and alkali resistance. It was clearly inferior in all of blackening resistance and yellowing resistance. Further, the film contains a metal compound (D) (that is, a compound (D) containing at least one metal selected from Li, Mg, Al, Ca, Mn, Co, Ni, Zn, Sr, W, Ce and Mo). The metal material of Comparative Example 4 that does not contain) has insufficient blackening resistance. Further, the metal material of Comparative Example 6 treated with chromate (zinc chromium 3360H) was particularly inferior in alkali resistance.

Claims (15)

Cationic water-soluble or water-based emulsion urethane resin (A) (hereinafter referred to as cationic urethane resin (A)), a polycondensation product of a phenolic compound and an aldehyde and a cationic one (B) (hereinafter referred to as A cationic phenol polycondensate (B)), a zirconium compound (C), and at least one selected from Li, Mg, Al, Ca, Mn, Co, Ni, Zn, Sr, W, Ce and Mo. A metal surface treatment agent comprising a metal-containing compound (D) (hereinafter referred to as a metal compound (D)) in an aqueous medium. The metal surface treating agent according to claim 1, wherein at least one acid component (E) selected from an inorganic acid and an organic acid (hereinafter referred to as an acid component (E)) is blended. The metal surface treating agent of Claim 1 or 2 which mix | blended the vanadium compound (F). The metal surface treating agent according to any one of claims 1 to 3, wherein a silane coupling agent (G) is blended. The metal surface treatment agent according to any one of claims 1 to 4, wherein the silane coupling agent (G) is at least one selected from a silane coupling agent having an amino group and a silane coupling agent having an epoxy group. . The metal surface treating agent according to any one of claims 1 to 5, wherein the cationic urethane resin (A) is a cationic water-soluble or water-based emulsion urethane resin modified with silyl. The blending ratio of the cationic urethane resin (A) to the cationic phenol polycondensate (B) is (A) :( B) = 99: 1 to 1:99 as a solid content mass ratio. The metal surface treating agent of any one of -6. The blending ratio of the cationic urethane resin (A) and the cationic phenol polycondensate (B) is (A) :( B) = 99: 1 to 50:50 as a solid content mass ratio. The metal surface treating agent of any one of -7. The compounding ratio of the zirconium compound (C) is 0.1 to 20 parts by mass as zirconium with respect to 100 parts by mass of the total solid content of the cationic urethane resin (A) and the cationic phenol polycondensate (B). The metal surface treating agent according to any one of claims 1 to 8. The compounding ratio of the metal compound (D) is 0.01 to 10 parts by mass as the metal with respect to 100 parts by mass of the total solid content of the cationic urethane resin (A) and the cationic phenol polycondensate (B). The metal surface treating agent according to any one of claims 1 to 9. The mixing ratio of the acid component (E) is 1 to 30 as the acid component itself containing no water with respect to 100 parts by mass of the total solid content of the cationic urethane resin (A) and the cationic phenol polycondensate (B). It is a mass part, The metal surface treating agent of any one of Claims 1-10. The compounding ratio of the vanadium compound (F) is 0.01 to 20 parts by mass as vanadium with respect to 100 parts by mass of the total solid content of the cationic urethane resin (A) and the cationic phenol polycondensate (B). The metal surface treating agent according to any one of claims 1 to 11. The blending ratio of the silane coupling agent (G) is 0.5 to 30 mass as a solid content with respect to 100 mass parts of the total solid content of the cationic urethane resin (A) and the cationic phenol polycondensate (B). The metal surface treatment agent according to claim 1, wherein the metal surface treatment agent is a part. A surface treatment of a metal material, wherein a coating is formed on the surface of the metal material by applying the metal surface treatment agent according to any one of claims 1 to 13 to the surface of the metal material and then drying the coating. Method. A metal material having a film formed by using the surface treatment method according to claim 14.